Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks

ABSTRACT

Various embodiments of the invention disclose that the uptake of LiO i Pr in Mg 2 (dobdc) (dobdc 4− =1,4-dioxido-2,5-benzenedicarboxylate) followed by soaking in a typical electrolyte solution leads to a new solid lithium electrolyte Mg 2 (dobdc).0.35LiO i Pr.0.25LiBF 4 .EC.DEC. Two-point ac impedance data show a pressed pellet of this material to have a conductivity of 3.1×10 −4  S/cm at 300 K. In addition, the results from variable-temperature measurements reveal an activation energy of approximately 0.15 eV, while single-particle data suggest that intraparticle transport dominates conduction.

CROSS REFERENCE TO RELATED APPLICATIONS

This U.S. application claims priority to U.S. Provisional ApplicationSer. No. 61/682,091 filed Aug. 10, 2012, which application isincorporated herein by reference as if fully set forth in theirentirety.

STATEMENT OF GOVERNMENTAL SUPPORT

The invention described and claimed herein was made in part utilizingfunds supplied by the U.S. Department of Energy under Contract No.DE-AC02-05CH11231 between the U.S. Department of Energy and the Regentsof the University of California for the management and operation of theLawrence Berkeley National Laboratory. The government has certain rightsin this invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Electrolytes and lithium-ion batteries.

2. Brief Description of the Related Art

Due to their high energy density and operating potential, lithium-ionbatteries have been widely adopted in portable electronics. However, toenable their implementation in traction applications, such as forelectric vehicles, considerable improvements must still be made in termsof cost, energy and power density, manufacture, and safety. Advances inelectrode chemistries as well as the separator are needed to meet thosechallenges. Currently, macroporous polymer membranes swelled withlithium salts dissolved in organic carbonates are utilized as theseparator in lithium-ion batteries. The use of a liquid electrolyterestricts battery shape and processing, while also posing numeroussafety problems, due to the potential leakage of corrosive liquids andthe volatility and flammability of the electrolyte solvent.

Furthermore, the lack of rigidity for current battery separatorsprecludes the use of solid lithium as an anode, because repeated cyclingleads to lithium dendrites that can pierce the separator and cause cellfailure. In contrast, a rigid, solid separator could inhibit lithiumdendrite growth and allow the use of metallic lithium as an anode. Giventhe high theoretical capacity of lithium metal (3860 Ah/kg), and it'svery negative reduction potential (−3.04 V vs. SHE), such an advancewould enable tremendous gains in energy capacity.

Since the 1970s, salts dissolved in solid polyethers have beeninvestigated as solid electrolyte materials. However, the lowconductivities of such materials at room temperature (10⁻⁶ S/cm)currently prevent their use in battery applications. Other solid lithiumelectrolytes either display total conductivities that are also too lowor are poorly compatible with the battery electrodes.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing aspects and others will be readily appreciated by theskilled artisan from the following description of illustrativeembodiments when read in conjunction with the accompanying drawings.

FIG. 1 illustrates the structure of Mg₂(dobdc) according to anembodiment of the invention.

FIG. 2 depicts room-temperature conductivity measurements performed onpellets of this material according to an embodiment of the invention.

FIG. 3 illustrates Arrhenius-type activated behavior depicted asactivation energy versus temperature according to an embodiment of theinvention.

FIG. 4 illustrates a Nyquist plot of CuBTTri soaked in a 1M LiBF₄ in 1:1(v:v) ethylene carbonate: diethyl carbonate mixture according to anembodiment of the invention.

FIG. 5 illustrates a Nyquist plot of MOF-177 soaked in a 1M LiBF₄ in 1:1(v:v) ethylene carbonate: diethyl carbonate mixture according to anembodiment of the invention.

FIG. 6 illustrates Powder x-ray diffraction data for Mg₂(dobdc) assynthesized (bottom, black) and post-synthetically modified (top, red)according to an embodiment of the invention according to an embodimentof the invention.

FIG. 7 illustrates FT-IR spectra of Mg₂(dobdc) before (bottom, black)and after (top, red) post-synthetic modification with lithiumisopropoxide according to an embodiment of the invention.

FIG. 8 illustrates plate-like morphology of as-synthesized Mg₂(dobdc)according to an embodiment of the invention.

FIG. 9 illustrates a view of the Mg₂(dobdc) plate surface that grew onthe borosilicate surface according to an embodiment of the invention.

FIG. 10 illustrates a view of the Mg₂(dobdc) plate surface opposite theborosilicate glass according to an embodiment of the invention.

FIG. 11 illustrates a close-up view of Mg₂(dobdc) showing platelet edgeand surface opposite the glass surface side according to an embodimentof the invention.

FIG. 12 illustrates a Thermogravimetric analysis data for the newlithium electrolyte material under flowing N₂ according to an embodimentof the invention.

DETAILED DESCRIPTION

In the discussions that follow, various process steps may or may not bedescribed using certain types of manufacturing equipment, along withcertain process parameters. It is to be appreciated that other types ofequipment can be used, with different process parameters employed, andthat some of the steps may be performed in other manufacturing equipmentwithout departing from the scope of this invention. Furthermore,different process parameters or manufacturing equipment could besubstituted for those described herein without departing from the scopeof the invention.

These and other details and advantages of the present invention willbecome more fully apparent from the following description taken inconjunction with the accompanying drawings.

Metal-organic frameworks are a broad class of microporous solids thathave been investigated primarily for their gas adsorption properties, aswell as for possible applications in sensing, drug delivery, catalysis,and optoelectronics. Recently, studies of electronic and protonconductivity have also been reported. While the intercalation of lithiumions into such materials has been observed, and porous zeolites havebeen investigated as fillers in solid polymer lithium electrolytesystems, as well as stand-alone solid electrolytes operating at hightemperatures (>300° C.), there are no reports to date of the use ofmetal-organic frameworks as a lithium electrolyte for possible batteryseparator applications.

Referring to FIG. 1, various embodiments of the invention disclose thatthe incorporation of lithium isopropoxide (LiO^(i)Pr) into ametal-organic framework Mg₂(dobdc) (whereindobdc⁴⁻=1,4-dioxido-2,5-benzenedicarboxylate) with open metal cationsites (Mg²⁺ cation sites) can produce a solid with an ionic conductivityof greater than 10⁻⁴ S/cm at 300 K.

In our evaluation of metal-organic frameworks as lithium electrolytematerials, we tested the ionic conductivity attained upon uptake of acommon electrolyte solution within (Zn₄O)(btb)₂ (whereinbtb³⁻=benzenetrisbenzoate), H₃[(Cu₄Cl)₃(BTTri)₈] (whereinBTTri³⁻=benzenetristriazolate) and Mg₂(dobdc). Each compound was soakedin a 1 M solution of lithium tetrafluoroborate (LiBF₄) in a 1:1 mixtureof ethylene carbonate (EC) and diethyl carbonate (DEC), and theresulting materials were dried and pressed into pellets. The pelletswere then placed in a thermostatted press and their conductivities weremeasured via two-point ac impedance spectroscopy. A Solartron 1260frequency response analyzer connected to a Solartron 1296 dielectricinterface and blocking stainless steel electrodes were employed for thisprocess. The conductivity of each material was obtained by measuring thereal impedance of the semicircles of the Nyquist plots, and taking thegeometry of the pellets into account. The impregnated frameworks showedconductivities on the order of 10⁻⁹ to 10⁻⁶ S/cm (see FIG. 4). The mostpromising metal-organic framework is Mg₂(dobdc), which upon uptake ofthe electrolyte solution afforded a room temperature conductivity of1.8×10⁻⁶ S/cm. Although the most conductive of the materials wemeasured, this value still lies three orders of magnitude below what isdesired for a battery electrolyte (10⁻³ S/cm at ambient temperature)⁴and two orders of magnitude below what is considered the technologicallimit for a functional battery electrolyte (10⁻⁴ S/cm). Researchers havepreviously effected post-synthetic modifications of metal-organicframeworks via covalent modification of organic ligands, as well asthrough the grafting of neutral ligands onto open metal centers.

The structure of Mg₂(dobdc) consists of one-dimensional hexagonalchannels approximately 14 Å in diameter, and lined withcoordinatively-unsaturated Mg²⁺ cation sites (see FIG. 1). An embodimentof the invention demonstrates that the presence of these sitesfacilitates the uptake of a lithium alkoxide, leading to higher ionicconductivity. Here, the alkoxide anions preferentially binds the Mg²⁺ions of the framework, pinning them in place, while leaving the Li⁺cations relatively free to move along the channels. Moreover, variationof the alkyl group allows screening of the negative charge of the oxygenatom and modification of the pore content. Indeed, preliminarymeasurements showed grafting of Li^(i)OPr to give higher conductivitiesthan grafting of either lithium methoxide (LiOMe) or lithium ethoxide(LiOEt).

To perform the grafting, Mg₂(dobdc) was activated by heating undervacuum to remove all solvent, followed by soaking for two weeks with ahot solution of the Li^(i)OPr in hexanes (see FIG. 1). The solids werethen washed with hexanes and dried under reduced pressure. Infraredspectra of the resulting materials revealed the emergence of aliphaticC—H stretches at 3200 cm⁻¹, a new C—O stretch at 1080 cm⁻¹, and abroadening of what we assign to be an Mg—O stretch at 450 cm⁻¹ (see FIG.5). The results from elemental analyses are consistent with the formulaMg₂(dobdc).0.5LiO^(i)Pr. Subsequent soaking of the material in a 1 Msolution of LiBF₄ in a 1:1 mixture of EC and DEC, resulted in uptake of0.25 equiv of lithium tetrafluoroborate (LiBF₄) and 2 equiv of carbonatesolvent (either EC or DEC) to give a compound of formulaMg₂(dobdc).0.35LiO^(i)Pr.0.25LiBF₄.EC.DEC. The decrease in LiO^(i)Prcontent may be due to leaching of unbound lithium alkoxide and/orexchange with LiBF₄. It should be noted that in concentrated solutionsLi⁺ cations can be solvated by as few as two carbonate molecules.²²Powder x-ray diffraction data for this material indicate that theframework structure is preserved throughout the impregnation process(see FIG. 6). Thus, within the pores of the framework, we find a highdensity of charge carriers in close proximity to each other, allowingLi⁺ cations to hop from site to site whilst remaining solvated by thecarbonate molecules. The final sample was obtained as a dry,free-flowing powder that could be readily pressed into pellets.

Measurements performed on pellets of this material from multiplepreparations afforded room-temperature conductivities falling in therange 0.9-4.4×10⁻⁴ S/cm (see FIG. 2). These values are two orders ofmagnitude greater than the 1.8×10⁻⁶ S/cm measured for a pellet ofMg₂(dobdc).0.05LiBF₄.xEC/DEC, as obtained by simply soaking Mg₂(dobdc)in a LiBF₄ electrolyte solution. Evaluation of the molar conductivitiesfor these two materials shows that, in addition to increasing lithiumelectrolyte content by a factor of 6.8, the grafting increases molarconductivity by a factor of 25, leading to the 170-fold increase inconductivity (see Table 1). Note that it is not possible to resolvegrain vs. grain boundary conduction within a pellet by examination ofthe Nyquist plots, since only one semicircle is observed in each dataset. However, the data do not form complete, regular semicircles,indicating the presence of inhomogeneities in the conduction pathway andtherefore possible multiple conduction mechanisms, albeit with similartime constants.²⁴

TABLE 1 Conductivity, Molar Li⁺ Concentration, Molar Conductivity, andActivation Energy for Pellets of Mg₂(dobdc) with Various ElectrolyteLoadings σ c_(Li) ⁺ Λ_(M) E_(a) electrolyte loading (S/cm) (M) (S ·cm⁻¹M⁻¹) (eV) 0.05LiBF₄ 1.8 × 10⁻⁶ 0.19 9.6 × 10⁻⁶ 0.31 0.06LiO^(i)Pr1.2 × 10⁻⁵ 0.23 5.2 × 10⁻⁵ 0.14 0.35LiO^(i)Pr + 0.25LiBF₄ 3.1 × 10⁻⁴ 1.32.4 × 10⁻⁴ 0.15

Varying the temperature of the pellets during the measurements revealedArrhenius-type activated behavior (see FIG. 3). The data indicate a lowactivation barrier of 0.15 eV for conduction in the grafted material. Incontrast, a much higher activation energy of 0.31 eV is observed for thematerial incorporating just LiBF₄, suggesting a fundamental differencein the conduction mechanism. As a solid electrolyte with 10⁻⁴ S/cmconductivity and an activation energy of less than 0.4 eV, the newisopropoxide-grafted material can be classified as a superionicconductor.²³

To probe the role of LiBF₄ in the conductivity of the new electrolyte,we prepared pellets of a sample of Mg₂(dobdc) incorporating LiO^(i)Prand the EC/DEC solvent, but with no LiBF₄ added. Variation of thegrafting conditions enabled preparation ofMg₂(dobdc).0.06LiO^(i)Pr.xEC/DC, for which the Li⁺ concentration isapproximately the same as in Mg₂(dobdc).0.05LiBF₄.xEC/DEC. For pelletsof the new isopropoxide grafted sample, a typical conductivity of1.2×10⁻⁵ S/cm was obtained (FIG. 2 c); however, considerable variationwas observed here, with results sometimes being as low as 10⁻⁷ S/cm. Wespeculate that without the presence of additional LiBF₄ on the surfacesof the metal-organic framework crystallites, it may be difficult toobtain good interparticle conductivity, as well as reproducibleinterfacial contacts between the pressed pellet and the electrodes. Thisobservation is consistent with other reports on the measurement ofconductivities of solid electrolytes.²⁵ Importantly, despite the lowerconductivity values, the activation energy of 0.14 eV for this sample issimilar to that obtained for Mg₂(dobdc).0.35LiO^(i)Pr.0.25LiBF₄.EC.DEC.

While the impedance measurements were unable to distinguish intra- vs.interparticle conduction, a peculiarity of Mg₂(dobdc) crystallite growthprovided a means of probing intraparticle conductivity. The compound canbe formed as polycrystalline solid thin films in which the channel axes,along which ionic transport would be expected, are oriented normal tothe film.²⁶ Indeed, SEM imaging showed our preparations to affordmaterial mainly of this form (see FIG. 8), as grown on the surface ofthe borosilicate glass vials. A free-standing sheet of one of thesefilms with the dimensions 1 mm×2 mm×0.4 mm was isolated and subjected tothe same grafting and lithium electrolyte soaking treatment as used inpreparation of the bulk solid electrolyte. AC impedance measurementsperformed directly on the film revealed a conductivity of 5.5×10⁻⁵ S/cm(see FIG. 2 d), which is of the same order of magnitude as obtained forpressed pellets of the bulk material. This result suggests thatintraparticle processes rather than boundary processes dominate theconduction. It is possible that alignment of the conduction channels inthe polycrystalline particles may even help to increase conductivity,since studies of lithium conductivity in polymers with anisotropicdomains have revealed strong alignment and orientation effects. Theattainability of thin, oriented films could perhaps facilitatedevelopment of methods for processing the new solid electrolyte andintegrating it within devices.

The foregoing results demonstrate a promising new approach for creatingsolid lithium electrolyte materials. Incorporation of a lithium alkoxidewithin a porous metal-organic framework with open metal centers, such asMg₂(dobdc), can lead to pinning of the counteranions and high ionicconductivities at ambient temperatures. The resulting conductivityvalues of 10⁻⁴ S/cm are highly reproducible, and are at thetechnological limit for battery separator applications. Efforts areunderway to elucidate the mechanisms of ionic conduction within the newelectrolyte material, and to obtain Li⁺ ion mobilities and transferencenumbers via dc polarization transference measurements and ⁷Li NMRdiffusion measurements. In addition, the performance of this materialupon cycling within a lithium battery cell will be evaluated.

General Considerations.

Unless otherwise specified all syntheses and sample manipulations wereperformed under the rigorous exclusion of air and moisture in either N₂or Ar glove boxes. All reagents and solvents were commercially availableand used without further purification. Infrared spectra were collectedon a Perkin Elmer Spectrum FT-IR/FT-FIR spectrometer equipped with anattenuated total reflectance accessory (ATR). Powder X-ray diffractiondata was collected using Cu Kα (λ=1.5406 Å) radiation on a Bruker D8Advance diffractometer. Carbon, hydrogen, and nitrogen analyses wereobtained from the Microanalytical Laboratory of the University ofCalifornia, Berkeley. Mass spectra were obtained from the QB3/ChemistryMass Spectrometry Facility at UC Berkeley. Metals and halogen analyseswere performed by Galbraith Laboratories in Knoxville, Tenn. SEM wasperformed at the University of California Robert D. Ogg ElectronMicroscope Lab on a Hitachi S-5000 SEM. TGAs were performed on TAInstruments TGA-Q500 under N₂ atmosphere at a heating rate of 0.5°C./min.

Synthesis and Activation of Mg₂(dobdc).

Solid portions of 0.666 g of H₄dobdc (3.36 mmol) and 2.730 g ofMg(NO₃)₂.6H₂O (10.6 mmol) were dissolved in a 15:1:1 (v:v:v) mixture ofDMF, ethanol, and deionized water. The solution was distributed amongst24 20-mL scintillation vials and capped with PTFE caps. The vials wereheated at 120° C. for 12 h. The resulting solid was collected over aBuchner funnel, dried under vaccum for 12 h, and transferred into aglove box. The sample was then soaked in DMF at 100° C. for 6 8-h cyclesand then soaked in anhydrous methanol for 6 8-h cycles. The sample wasthen filtered and transferred into a Schlenk flask where it wasevacuated at <10 mtorr for 12 h at 250° C.

Lithium Isopropoxide Grafting of Mg₂(dobdc) in Hexanes.

The activated framework was reacted with a 10-fold molar excess of 1.0 Mlithium isopropoxide in hexanes in sealed vials at 80° C. for 2 weeks,after which the sample was collected by filtration and washed repeatedlywith hexanes. The sample was then transferred to a Schlenk flash andevacuated on a vacuum line at <10 mtorr for 24 h at 180° C. MetalsAnalysis—Mg: 12.9%, Li: 0.970%. Molar ratio of Mg:Li—2:0.53. Elementalanalysis—Calculated C: 41.45; H: 2.05; Found C: 40.61; H: 2.90.

Mg₂(dobdc).0.35LiO^(i)Pr.0.25LiBF₄.EC.DEC.

The material obtained as described above was soaked for 24 h in a 1 MLiBF₄ solution in a 1:1 (v:v) mixture of ethylenecarbonate (EC) anddiethylcarbonate (DEC). Metals and halogen analysis (weight percent)—Mg:9.10%, Li: 0.780%, B: 0.506%, F: 3.55%. Molar ratio ofMg:Li:B:F—2:0.6:0.25:1. Elemental analysis—Calculated (based on metalsand halogen analysis) C: 39.19; H: 2.29; Found C: 37.72; H: 3.88. Theobtained C, H, and N analyses poorly fit the formula calculated from themetals analysis. We believe this to be due to solvent desorption andpossible uptake of other solvents in the glove box prior to analysis.Thermogravimetric analysis data of the material freshly removed from asealed vial is consistent with the loss of one EC and one DEC molecule(45% weight loss).

Mg₂(dobdc).0.06LiO^(i)Pr.xEC.yDEC.

The activated framework was reacted with a 10-fold molar excess of 1.0 Mlithium isopropoxide in tetrahydrofuran in sealed vials at 80° C. for 2weeks, after which the sample was filtered and washed repeatedly withtetrahydrofuran. The sample was then transferred to a Schlenk flash anddesolvated by heating on a vacuum line at 180° C. and <10 mtorr for 24h. The material was then soaked for 24 h in a 1:1 (v:v) mixture of ECand DEC. Metals analysis (weight percent)—Mg:13.79%, Li 0.0723%. Molarratio of Mg:Li—2:0.06.

Mg₂(dobdc).0.05LiBF₄.xEC.yDEC.

An activated sample of Mg₂(dobdc) was soaked for 24 h in a 1 M LiBF₄solution in a 1:1 (v:v) ethylene carbonate:diethyl carbonate solution.Metals and halogen analysis (weight percent)—Mg:11.3%, Li: 0.082%, B:0.069%, F: 0.858%. Molar ratio of Mg:Li:B:F—2—0.05:0.05:0.2.

Pellet Pressing.

Within an argon-filled glove box, the electrolyte material was placed ina Kapton washer and sandwiched between PTFE sheets. The pellet was thenpressed at 5000 psi for 1 min. Conductivity Measurements.

In an argon-filled glove box, ac impedance spectroscopy measurementswere made using a homemade test cell on thermostatted pressed samplesusing a Solartron 1260 frequency response analyzer connected to aSolartron 1296 dielectric interface and blocking stainless steelelectrodes. SMART (v1.1.1) software was used as control software.Measurements were made over a frequency range of 1 MHz to 1 Hz using a100 mV (peak voltage) applied ac signal. Ten measurements were made inevery frequency decade with 1 s integration times at each frequency.Variable temperature impedance spectra were collected over manytemperatures using the thermostatted temperature control. Ionicconductivity σ (S/cm) was calculated as:

σ=L/(AR)

where L is the pellet thickness and A is the area in contact with theelectrodes and R is the real impedance measured from the location of thelocal minima between the high and low frequency arcs measured on thereal axis of a Nyquist plot. We found extrapolation of the highfrequency arc to the real frequency intercept did not give conductivityvalues significantly different from the real resistance value measuredat the local minima. We also found the values to not significantlydiffer when obtained by finding the plateau region of the Bode plot (log|Z| vs. log f). For example the measured resistance of a pellet made ofMg₂(dobdc).0.35LiO^(i)Pr.0.25LiBF₄.EC.DEC was 2049 Ω measuring by thelocal minima method, 2189 Ω by modeling the high frequency curve as apolynomial and finding the real resistance axis intercept and by findingthe plateau region of the Bode plot 2010 Ω.

This invention has been described herein to provide those skilled in theart with information relevant to apply the novel principles and toconstruct and use such specialized components as are required. However,it is to be understood that the invention can be carried out bydifferent equipment, materials and devices, and that variousmodifications, both as to the equipment and operating procedures, can beaccomplished without departing from the scope of the invention itself.

Design, analysis, description of the materials used, properties of, andthe synthesis of the Solid Lithium Electrolyte is described in thepapers entitled A Solid Lithium Electrolyte via Addition of LithiumIsopropoxide to a Metal-Organic Framework with Open Metal Sites andsupporting information of the same. These papers are incorporated hereinby reference as if fully set forth in their entirety.

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We claim:
 1. A composition comprising: a metal-organic framework; and a lithium alkoxide.
 2. The composition of claim 1, wherein the metal-organic framework comprises Mg₂(dobdc), wherein dobdc⁴⁻=1,4-dioxido-2,5-benzenedicarboxylate.
 3. The composition of claim 1, wherein the lithium alkoxide comprises lithium isopropoxide (LiO^(i)Pr).
 4. The composition of claim 1, wherein the lithium alkoxide comprises lithium ethoxide (LiOEt).
 5. The composition of claim 1, wherein the lithium alkoxide comprises lithium methoxide LiOMe)
 6. The composition of claim 1, wherein metal-organic framework comprises open metal cation Mg²⁺ sites.
 7. The composition of claim 1, wherein metal-organic framework further comprises lithium tetrafluoroborate (LiBF₄)
 8. The composition of claim 1, wherein metal-organic framework further comprises ethylene carbonate (EC).
 9. The composition of claim 1, wherein metal-organic framework further comprises diethyl carbonate (DEC)
 10. The composition of claim 1 comprising Mg₂(dobdc).0.35LiO^(i)Pr.0.25LiBF₄. EC.DEC.
 11. A method of forming a composition including a metal-organic framework and a lithium alkoxide comprising: dissolving solid portions of H₄dobdc and Mg(NO₃)₂.6H₂O in a mixture of DMF, ethanol, and deionized water and heating the solution to produce a solid; soaking the resulting solid in DMF and then soaking in anhydrous methanol followed by filtering and evacuating the resultant solid to form an activated framework; reacting the activated framework with lithium isopropoxide in hexanes and collecting the sample by filtration and washing repeatedly with hexanes followed by evacuation; and soaking the activated framework in a lithium tetrafluoroborate (LiBF₄) solution including a mixture of ethylenecarbonate (EC) and diethylcarbonate (DEC).
 12. The method of claim 11, wherein the metal-organic framework comprises Mg₂(dobdc), wherein dobdc⁴⁻=1,4-dioxido-2,5-benzenedicarboxylate.
 13. The method of claim 11, wherein the lithium alkoxide comprises lithium isopropoxide (LiO^(i)Pr).
 14. The method of claim 11, wherein the lithium alkoxide comprises lithium ethoxide LiOEt).
 15. The method of claim 11, wherein the lithium alkoxide comprises lithium methoxide (LiOMe)
 16. The method of claim 11, wherein metal-organic framework comprises open metal cation Mg²⁺ sites.
 17. The method of claim 11, wherein metal-organic framework further comprises lithium tetrafluoroborate (LiBF₄).
 18. The method of claim 11, wherein metal-organic framework further comprises ethylene carbonate (EC).
 19. The method of claim 11, wherein metal-organic framework further comprises diethyl carbonate (DEC)
 20. The method of claim 11, wherein the composition comprises Mg₂(dobdc).0.35LiO^(i)Pr.0.25LiBF₄.EC.DEC. 